Ester Compound and Its Use

ABSTRACT

An ester compound represented by the formula (1): 
     
       
         
         
             
             
         
       
     
     has excellent pest controlling activity and is useful as an active ingredient for a pest controlling agent.

TECHNICAL FIELD

The present invention relates to an ester compound and its use.

BACKGROUND ART

EP 0196156 A1 describes certain fluorobenzyl ester compounds as anactive ingredient of insecticides. However, the insecticidal activity ofthe fluorobenzyl ester compounds is not necessarily sufficient.

DISCLOSURE OF THE INVENTION

As a result of the intensive study to find a compound having excellentpest controlling activity, the present inventor has found that acompound represented by the formula (1) has excellent pest controllingactivity, and has completed the present invention.

That is, the present invention provides an ester compound represented bythe formula (1):

(hereinafter, referred to as the present compound), a pest controllingagent comprising the present compound as an active ingredient, and amethod for controlling pests by applying an effective amount of thepresent compound to pests or a place where pests inhabit.

MODE OF CARRYING OUT THE INVENTION

There are isomers of the present compound, originated from twoasymmetric carbon atoms on the cyclopropane ring, and from the doublebond. The present invention includes each active isomer and an activemixture of the isomers at any ratio thereof.

Examples of the existing form of the present compound include thosedescribed below:

a compound of the formula (1), in which the absolute configuration of1-position of the cyclopropane ring is the R-configuration;a compound of the formula (1), in which the relative configuration ofthe substituents at 1-position and at 3-position of the cyclopropanering is the trans configuration;a compound of formula (1), in which the relative configuration of thesubstituents at 1-position and at 3-position of the cyclopropane ring isthe cis configuration;a compound of formula (1), in which the relative configuration of thedouble bond of the substituent at 3-position of the cyclopropane ring isthe Z-configuration;a compound of formula (1), in which the absolute configuration of1-position of the cyclopropane ring is the R-configuration and therelative configuration of the substituents at 1-position and at3-position of the cyclopropane ring is the trans configuration;a compound of formula (1), in which the absolute configuration of1-position on the cyclopropane ring is the R-configuration and therelative configuration of the substituents at 1-position and at3-position of the cyclopropane ring is the cis configuration;a compound of formula (1), in which the absolute configuration of1-position on the cyclopropane ring is R-configuration, the relativeconfiguration of the substituents at 1-position and at 3-position of thecyclopropane ring is the trans configuration and the relativeconfiguration of the double bond of the substituent at 3-position of thecyclopropane ring is the Z-configuration;a compound of formula (1), in which the absolute configuration of1-position on the cyclopropane ring is the R-configuration, the relativeconfiguration of the substituents at 1-position and at 3-position of thecyclopropane ring is the cis configuration and the relativeconfiguration of the double bond of the substituent at 3-position of thecyclopropane ring is the Z-configuration;a compound of formula (1) rich in an isomer, in which the absoluteconfiguration of 1-position on the cyclopropane ring is theR-configuration and the relative configuration of the substituents at1-position and at 3-position of the cyclopropane ring is the transconfiguration;a compound of formula (1) containing 80% or more of an isomer, in whichthe absolute configuration of 1-position on the cyclopropane ring is theR-configuration and the relative configuration of the substituents at1-position and at 3-position of the cyclopropane ring is the transconfiguration; anda compound of formula (1) containing 90% or more of an isomer, in whichthe absolute configuration of 1-position on the cyclopropane ring is theR-configuration and the relative configuration of the substituents at1-position and at 3-position of the cyclopropane ring is the transconfiguration.

The present compound can be prepared, for example, by the followingproduction method. The method reacting an alcohol compound representedby the formula (2)

with a carboxylic acid compound represented by the formula (3)

or a reactive derivative thereof (e.g., acid halide, acid anhydride,etc.).

This reaction is usually carried out in a solvent in the presence of acondensing agent or a base.

Examples of the condensing agent include dicyclohexylcarbodiimide and1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride.

Examples of the base include organic bases such as triethylamine,pyridine, N,N-diethylaniline, 4-dimethylaminopyridine,diisopropylethylamine, etc.

Examples of the solvent include hydrocarbons such as benzene, toluene,hexane, etc.; ethers such as diethyl ether, tetrahydrofuran, etc.;halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane,chlorobenzene, etc.; and the like.

The reaction time is usually within the range of 5 minutes to 72 hours.

The reaction temperature is usually within the range of −20° C. to 100°C. (provided that, when a solvent used has a boiling point below 100°C., −20° C. to the boiling point of the solvent), preferably −5° C. to100° C. (provided that, when a solvent used has a boiling point below100° C., −5° C. to the boiling point of the solvent).

The reaction can be carried out at any molar ratio of the alcoholcompound of the formula (2) to the carboxylic acid compound of theformula (3) or a reactive derivative thereof, but preferably at a ratioof one mole to one mole or around this ratio.

The condensing agent or the base can be used in any ratio usually in therange of one mole to an excess amount, preferably one to five moles,relative to one mole of the alcohol compound of the formula (2). Thecondensing agent or the base is appropriately selected depending on aparticular kind of the carboxylic acid compound of the formula (3) or areactive derivative thereof.

After the reaction has been completed, the present compound can beisolated by carrying out a conventional post-treatment operation such asfiltration of a reaction mixture, followed by concentrating thefiltrate, or to pour a reaction mixture into water, followed byextracting with an organic solvent and concentrating the extract. Theisolated present compound can be further purified by chromatography,distillation, or the like.

The alcohol compound of the formula (2) is described, for example, in EP0196156 A1, and can be prepared according to the method describedtherein.

The carboxylic acid compound of the formula (3) is described, forexample, in Agr. Biol. Chem., 34, 1119 (1970) and can be preparedaccording to the method described therein.

Examples of pests controlled by the present compound include arthropodssuch as insects, acarines, and the like. Specific examples are thosedescribed below.

Lepidoptera:

Pyralid moths (Pyralidae) such as rice stem borer (Chilo suppressalis),rice leafroller (Cnaphalocrocis medinalis), Indian meal moth (Plodiainterpunctella), and the like, owlet moths (Noctuidae) such as commoncutworm (Spodoptera litura), rice armyworm (Pseudaletia separata),cabbage armyworm (Mamestra brassicae), and the like, whites (Pieridae)such as common cabbageworm (Pieris rapae), and the like, tortricid moths(Tortricidae) such as Adoxophyes orana, and the like, Carposimidae,lyonetiid moths (Lyonetiidae), tussock moths (Lymantriidae), Autographa,Agrotis spp. such as cutworm (Agrotis segetum), black cutworm (Agrotisipsilon), and the like, Helicoverpa spp., Heliothis spp., diamondback(Plutella xylostella), rice skipper (Parnara guttata), casemakingclothes moth (Tinea pellionella), webbing clothes moth (Tineolabisselliella), and the like;

Diptera:

Mosquitos (Calicidae) such as common mosquito (Culex pipiens pallens),Culex tritaeniorhynchus, and the like, Aedes spp. such as Aedes aegypti,Aedes albopictus, and the like, Anopheles such as Anopheles sinensis andthe like, midges (Chironomidae), house flies (Muscidae) such as housefly(Musca domestica), false stablefly (Muscina stabulans), lesser housefly(Fannia canicularis), and the like, Calliphoridae, Sarcophagidae,anthomyiid flies (Anthomyiidae) such as seedcorn maggot (Hylemyaplatura), onion maggot (Delia antiqua), and the like, fruit flies(Tephritidae), small fruit flies (Drosophilidae), moth flies(Psychodidae), Phoridae, black flies (Simuliidae), Tabanidae, stableflies (Stomoxyidae), Ceratopogonidae, and the like;

Blattodea:

German cockroach (Blattella germanica), smokybrown cockroach(Periplaneta fuliginosa), American cockroach (Periplaneta americana),brown cockroach (Periplaneta brunnea), oriental cockroach (Blattaorientalis) and the like;

Hymenoptera:

Ants (Formicidae), hornets, yellow jackets and potter wasps (Vespidae),bethylid wasps, sawflies (Tenthredinidae) such as cabbage sawfly(Athalia rosae japonensis), and the like;

Aphaniptera:

Ctenocephalides canis, Ctenocephalides felis, Pulex irritans and thelike;

Anoplura:

Pediculus humanus, Phthirus pubis, Pediculus humanus humanus, Pediculushumanus corporis, and the like;

Isoptera:

Reticulitermes speratus, Coptotermes formosanus, and the like;

Hemiptera:

Planthoppers (Delphacidae) such as small brown planthopper (Laodelphaxstriatellus), brown rice planthopper (Nilaparvata lugens), white-backedrice planthopper (Sogatella furcifera), and the like, leafhoppers(Deltocephalidae) such as green rice leafhopper (Nephotettixcincticeps), green rice leafhopper (Nephotettix virescens), and thelike, aphids (Aphididae), stink bugs (Pentatomidae), whiteflies(Aleyrodidae), scales (Coccidae), lace bugs (Tingidae), psyllids(Psyllidae), and the like;

Coleoptera:

Corn rootworm (Diabrotica spp.) such as Attagenus japonicus, Anthrenusverbasci, western corn rootworm (Diabrotica virgifera), southern cornrootworm (Diabrotica undecimpunctata howardi), and the like, scarabs(Scarabaeidae) such as cupreous chafer (Anomala cuprea), soybeen beetle(Anomala rufocuprea), and the like, weevils (Curculionidae) such asmaize weevil (Sitophilus zeamais), rice water weevil (Lissorhoptrusoryzophilus), cottonseed weevil (Anthonomus gradis gradis), adzuki beenweevil (Callosobruchuys chienensis), and the like, darkling beetles(Tenebrionidae) such as yellow mealworm (Tenebrio molitor), red flourbeetle (Tribolium castaneum), and the like, leaf beetles (Chrysomelidae)such as rice leaf beetle (Oulema oryzae), striped flea beetle(Phyllotreta striolata), cucurbit leaf beetle (Aulacophora femoralis),and the like, drugstore beetles (Anobiidae), Epilachna spp. such astwewnty-eight-spotted ladybird (Epilachna vigintioctopunctata), and thelike, powder post beetles (Lyctidae), false powder post beetles(Bostrychidae), longhorn beetles (Cerambycidae), rove beetle (Paederusfuscipes), and the like;

Thysanoptera:

Thrips palmi, Frankliniella occidentalis, flower thrips (Thripshawaiiensis), and the like;

Orthoptera:

Mole crickets (Gryllotalpidae), grasshoppers (Acrididae), and the like;

Acarina:

House dust mites (Epidermoptidae) such as Dermatophagoides farinae,Dermatophagoides ptrenyssnus, and the like, acarid mites (Acaridae) suchas mold mite (Tyrophagus putrescentiae), brown legged grain mite(Aleuroglyphus ovatus), and the like, Glycyphagidae such as Glycyphagusprivatus, Glycyphagus domesticus, groceries mite (Glycyphagusdestructor), and the like, cheyletid mites (Cheyletidae) such asCheyletus malaccensis, Cheyletus fortis, and the like, Tarsonemidae,Chortoglyphidae, Haplochthoniidae, spider mites (Tetranychidae) such astwo-spotted spider mite (Tetranychus urticae), Kanzawa spider mite(Tetranychus kanzawai), citrus red mite (Panonychus citri), European redmite (Panonychus ulmi), and the like; and hard ticks (Ixodidae) such asHaemaphysalis longicornis, and the like.

The pest controlling agent of the present invention may be the presentcompound itself or, usually, may be a formulation of the presentcompound.

Examples of the formulation include oil solutions, emulsifiableconcentrates, wettable powders, flowable formulations (e.g. aqueoussuspension and aqueous emulsion), dusts, granules, aerosols, volatileformulations by heating (e.g. mosquito-coil, mosquito-mat for electricheating and volatile formulations with absorptive wick for heating),heating fumigants (e.g. self-burning type fumigants, chemical reactiontype fumigants and porous ceramic plate fumigant), non-heating volatileformulations (e.g. resin volatile formulations and impregnated papervolatile formulations), smoking formulations (e.g. fogging), ULVformulations and poisonous baits.

The formulation can be prepared, for example, by the following methods:

(1) mixing the present compound with a liquid and/or gaseous carrier,and optionally adding a surfactant and other auxiliaries for aformulation;(2) mixing the present compound with a powdery solid carrier, andoptionally adding a surfactant and other auxiliaries for a formulation;and(3) impregnating a shaped solid carrier with the present compound; ormixing the present compound with a powdery solid carrier, and optionallyadding a surfactant and other auxiliaries for a formulation, and shapingthe resulting mixture.

A content of the present compound depends on a particular type offormulations but, usually, these formulations can contain 0.001 to 95%by weight of the present compound.

Examples of the carrier used for the formulation include solid carrierssuch as clays (e.g. kaolin clay, diatomaceous earth, synthetic hydratedsilicon oxide, bentonite, Fubasami clay and acid clay), talc and thelike, ceramics, other inorganic minerals (e.g. sericite, quartz, sulfur,active carbon, calcium carbonate, hydrated silicon oxide andmontmorillonite) and chemical fertilizers (e.g. ammonium sulfate,ammonium phosphate, ammonium nitrate, urea and ammonium chloride);liquid carriers such as water, alcohols (e.g. methanol and ethanol),ketones (e.g. acetone and methyl ethyl ketone), aromatic hydrocarbons(e.g. benzene, toluene, xylene, ethylbenzene, methylnaphthalene andphenylxylylethane), aliphatic hydrocarbons (e.g. hexane, cyclohexane,kerosene and gas oil), esters (e.g. ethyl acetate and butyl acetate),nitrites (e.g. acetonitrile and isobutyronitrile), ethers (e.g.diisopropyl ether and dioxane), acid amides (e.g. N,N-dimethylformamideand N,N-dimethylacetamide), halogenated hydrocarbons (dichloromethane,trichloroethane and carbon tetrachloride), dimethyl sulfoxide andvegetable oils (e.g. soybean oil and cottonseed oil); and gaseouscarriers such as chlorofluorocarbon gas, butane gas, LPG (liquefiedpetroleum gas), dimethyl ether and carbon dioxide gas.

Examples of the surfactant include alkyl sulfate esters, alkylsulfonatesalts, alkylarylsulfonate salts, alkyl aryl ethers, polyoxyethylenatedalkyl aryl ethers, polyethylene glycol ethers, polyhydric alcohol estersand sugar alcohol derivatives.

Examples of the other auxiliaries for a formulation include stickingagents, dispersing agents and stabilizers, typically casein, gelatin,polysaccharides (e.g. starch, gum arabic, cellulose derivatives andalginic acid), lignin derivatives, bentonite, synthetic water-solublepolymers (e.g. polyvinyl alcohol and polyvinylpyrrolidone), polyacrylicacid, BHT (2,6-di-tert-butyl-4-methyphenol) and BHA (mixture of2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol).

Examples of the solid carrier for a mosquito-coil include a mixture ofraw plant powder such as wood powder and Pyrethrum marc and a bindingagent such as Tabu powder (powder of Machilus thunbergii), starch orgluten.

Examples of the shaped solid carrier for a mosquito-mat for electricheating include plates of compacted fibrils of cotton linters and of amixture of pulp and cotton linters.

Examples of the solid carrier for the self-burning type fumigantincludes exothermic combustion agents such as nitrate, nitrite,guanidine salt, potassium chlorate, nitrocellulose, ethylcellulose andwood powder, pyrolytic stimulating agents such as alkali metal salts,alkaline earth metal salts, dichromates and chromates, oxygen sourcessuch as potassium nitrate, combustion assistants such as melanin andwheat starch, bulk fillers such as diatomaceous earth and binding agentssuch as synthetic glue.

Examples of the solid carrier for a chemical reaction type fumigantinclude exothermic agents such as alkali metal sulfides, polysulfides,hydrogensufides and calcium oxide, catalytic agents such as carbonaceoussubstances, iron carbide and activated clay, organic foaming agents suchas azodicarbonamide, benzenesulfonyl hydrazide, dinitrosopentamethylenetetramine, polystyrene and polyurethane and fillers such as natural andsynthetic fibers.

Examples of the solid carrier for a non-heating volatile formulationinclude thermoplastic resins and paper such as filter paper and Japanesepaper.

Examples of the base material for a poisonous bait include baitingredients such as grain powder, vegetable oil, sugar and crystallinecellulose, antioxidants such as dibutyl hydroxytoluene andnordihydroguaiaretic acid, preservatives such as dehydroacetic acid,substances for preventing children and pets from erroneous eating suchas red pepper powder, pest-attractant flavorants such as cheeseflavorant, onion flavorant and peanut oil.

The method for controlling pests of the present invention is usuallycarried out by applying the pest controlling agent of the presentinvention containing an effective amount of the present compound topests or a place where pests inhabit.

The formulation of the pest controlling agent of the present inventionis applied, for example, by the following methods:

(1) applying the formulation as such to pests or a place where pestsinhabit;(2) spraying the formulation in the form of a diluted solution with asolvent such as water to pests or a place where pests inhabit; in thiscase, a concentration of the active ingredient in the diluted solutionis usually 0.1 to 10000 ppm, or(3) volatilizing the active ingredient by heating the formulation at aplace where pests inhabit.

These methods can be appropriately selected according to a particulartype of the agent, application place, or the like.

In any method, the amount of the present compound to be applied can beappropriately determined according a particular form of the pestcontrolling agent of the present invention, time, place and method ofthe application, kind of the pests, damage, and the like. Usually, whenapplied on a plane, the amount is 1 to 10,000 mg per 1 m², and whenapplied in a space, the amount is 0.1 to 5,000 mg per 1 m³.

The pest controlling agent of the present invention can be used togetherwith or by mixing with other insecticides, nematocides, fungicides,herbicides, plant growth regulators, repellents, synergists, fertilizersand/or soil conditioners.

Examples of the active ingredients of the insecticide and acaricideinclude:

organophosphorus compounds such as fenitrothion, fenthion, diazinon,chlorpyrifos, acephate, methidathion, disulfoton, DDVP, sulprofos,cyanophos, dioxabenzofos, dimethoate, phenthoate, malathion,trichlorfon, azinphosmethyl, monocrotophos and ethion;

carbamate compounds such as BPMC, benfuracarb, propoxur, carbosulfan,carbaryl, methomyl, ethiofencarb, aldicarb, oxamyl and fenothiocarb;

pyrethroid compounds such as etofenprox, fenvalerate, esfenvalerate,fenpropathrin, cypermethrin, permethrin, cyhalothrin, deltamethrin,cycloprothrin, fluvalinate, bifenthrin,2-methyl-2-(4-bromodifluoromethoxyphenyl)propyl (3-phenoxybenzyl)ether,tralomethrin, silafluofen, d-phenothrin, cyphenothrin, d-resmethrin,acrinathrin, cyfluthrin, tefluthrin, transfluthrin, tetramethrin,allethrin, d-furamethrin, prallethrin, empenthrin and5-(2-propynyl)furfuryl 2,2,3,3-tetramethylcyclopropanecarboxylate;

nitroimidazolidine derivatives; N-cyanoamidine derivatives such asacetamiprid; chlorinated hydrocarbon compounds such as endosulfan, γ-BHCand 1,1-bis(chlorophenyl)-2,2,2-trichloroethanol; benzoylphenylureacompounds such as chlorfluazuron, teflubenzuron and flufenoxuron;phenylpyrazole compounds; metoxadiazon; bromopropylate; tetradifon;chinomethionat; pyridaben; fenpyroximate; diafenthiuron; tebufenpyrad;polynactins complex such as tetranactin, dinactin and trinactin;pyrimidifen; milbemectin; abamectin; ivermectin; and azadirachtin.

Examples of the repellent include 3,4-caranediol,N,N-diethyl-m-toluamide, 1-methylpropyl2-(2-hydroxyethyl)-1-piperidinecarboxylate, p-menthan-3,8-diol,botanical essential oils such as hyssop oil, and the like.

Examples of the synergist include bis(2,3,3,3-tetrachloropropyl)ether(S-421), N-(2-ethylhexyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide(MGK-264) and5-((2-(2-Butoxyethoxy)ethoxy)methyl)-6-propyl-1,3-benzodioxole(piperonyl butoxide).

The present invention will be further illustrated in detail by thefollowing Production Example, Formulation Examples and Test Examples.

First, the Production Example of the present compound will be described.

PRODUCTION EXAMPLE

Under nitrogen atmosphere, to a mixture of 0.20 g of4-propargyl-2,3,5,6-tetrafluorobenzyl alcohol, 0.17 g of(1R)-trans-3-(2-cyano-1-propenyl)-2,2-dimethylcyclopropanecarboxylicacid, 0.022 g of 4-dimethylaminopyridine in 7 ml of dichloromethane wasadded 0.21 g of N,N-dicyclohexylcarbodiimide, and the mixture wasstirred at room temperature for three hours. Then, the reaction mixturewas filtrated, and the filtrate was concentrated under reduced pressure.The resultant residue was subjected to silica gel column chromatographyto obtain 0.26 g of 4-propargyl-2,3,5,6-tetrafluorobenzyl(1R)-trans-3-(2-cyano-1-propenyl)-2,2-dimethylcyclopropanecarboxylate(hereinafter, referred to as the present compound (A)) represented bythe formula (A):

(an isomer ratio based on the double bond of the 2-cyano-1-propenylgroup: Z/E=about 2/1).

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.21 (s, 3H, Z+E forms), 1.32 (s, 3H, Z+Eforms), 1.72 (t, 1H, Z+E forms), 1.96 (s, 3H, Z+E forms), 2.06 (s, 1H,Z+E forms), 2.20 (m, 1/3H, E form), 2.47 (m, 2/3H, Z form), 3.64 (s, 2H,Z+E forms), 5.24 (s, 2H, Z+E forms), 5.78 (d, 2/3H, Z form), 6.00 (d,1/3H, E form)

Next, Formulation Examples will be described. Parts are by weight.

FORMULATION EXAMPLE 1

To a solution of 20 parts of the present compound (A) in 65 parts ofxylene is added 15 parts of Sorpol 3005X (registered trademark of TohoChemical Industry Co., LTD.), and the mixture is thoroughly mixed withstirring to obtain an emulsifiable concentrate.

FORMULATION EXAMPLE 2

To 40 parts of the present compound (A) is added 5 parts of Sorpol3005X, and the mixture is thoroughly mixed with stirring. To the mixtureare added 32 parts of Carplex #80 (synthetic hydrated silica, registeredtrademark of Shionogi & Co., Ltd.) and 23 parts of 300-mesh diatomaceousearth, and the resulting mixture is thoroughly mixed with a juice mixerto obtain a wettable powder.

FORMULATION EXAMPLE 3

A mixture of 1.5 parts of the present compound (A), 1 part of TokusilGUN (synthetic hydrated silica, manufactured by Tokuyama Corp.), 2 partsof Reax 85A (sodium ligninsulfonate, manufactured by Westvacochemicals), 30 parts of Bentonite Fuji (bentonite, manufactured by HojunCo.) and 65.5 parts of Shokozan A clay (kaolin clay, manufactured byShokozan Kogyosho Co.) is thoroughly pulverized. To the resultingmixture is added water, and the mixture is kneaded, granulated with apiston-granulator and dried to obtain a 1.5% granule.

FORMULATION EXAMPLE 4

A mixture of 10 parts of the present compound (A), 10 parts ofphenylxylylethane and 0.5 part of Sumidur L-75 (tolylenediisocyanatemanufactured by Sumika Bayer Urethane Co., Ltd.) is added to 20 parts of10% aqueous solution of gum arabic, and stirred with a homomixer toobtain an emulsion having a mean particle diameter of 20 μm. To this isadded 2 parts of ethylene glycol, and stirred for 24 hours on a waterbath at 60° C. to obtain microcapsule slurry. On the other hand, 0.2part of xanthan gum and 1.0 part of Veegum R (aluminum magnesiumsilicate manufactured by Sanyo Chemical Co., Ltd.) are dispersed in 56.3parts of ion-exchanged water to obtain a thickener solution. Amicroencapsulated formulation is obtained by mixing 42.5 parts of theabove microcapsule slurry and 57.5 parts of the thickener solution.

FORMULATION EXAMPLE 5

A mixture of 10 parts of the present compound (A) and 10 parts ofphenylxylylethane is added to 20 parts of 10% aqueous solution ofpolyethylene glycol, and the mixture is stirred with a homomixer toobtain an emulsion having a mean particle diameter of 3 μm. On the otherhand, 0.2 part of xanthan gum and 1.0 part of Veegum R (aluminummagnesium silicate manufactured by Sanyo Chemical Co., Ltd.) aredispersed in 58.8 parts of ion-exchanged water to give a thickenersolution. A flowable formulation is obtained by mixing 40 parts of theabove emulsion and 60 parts of the thickener solution.

FORMULATION EXAMPLE 6

A mixture of 5 parts of the present compound (A), 3 parts of Carplex #80(fine powder of synthetic hydrated silicon dioxide, trademark ofShionogi & Co., Ltd.), 0.3 part of PAP (mixture of monoisopropylphosphate and diisopropyl phosphate) and 91.7 parts of 300-mesh talc arestirred with a juice mixer to obtain a dust.

FORMULATION EXAMPLE 7

A solution of 0.1 part of the present compound (A) in 10 parts ofdichloromethane is mixed with 89.9 parts of deodorized kerosene toobtain an oil solution.

FORMULATION EXAMPLE 8

A solution of 1 part of the present compound (A), 5 parts ofdichloromethane and 34 parts of deodorized kerosene is filled in anaerosol vessel. A valve is attached to the vessel and 60 partspropellant (liquefied petroleum gas) is charged under pressure throughthe valve to obtain an oily aerosol.

FORMULATION EXAMPLE 9

A solution of 0.6 part of the present compound (A), 5 parts of xylene,3.4 parts of deodorized kerosene and 1 part of Atmos 300 (emulsifier,trademark of Atlas Chemical Co.) and 50 parts of water are filled in anaerosol vessel. A valve is attached to the vessel and 40 partspropellant (liquefied petroleum gas) is charged under pressure throughthe valve to obtain an aqueous aerosol.

FORMULATION EXAMPLE 10

A solution of 0.3 g of the present compound (A) in 20 ml of acetone isuniformly mixed with 99.7 g of a base material for a mosquito-coil(mixture of Tabu powder, Pyrethrum marc and wood powder at the ratio of4:3:3). To the mixture is added 100 ml of water and the resultingmixture is thoroughly kneaded, then molded and dried to obtain amosquito-coil.

FORMULATION EXAMPLE 11

A solution is prepared by adding acetone to 0.8 g of the presentcompound (A) and 0.4 g of piperonyl butoxide and adjusting to 10 ml. Abase material (a plate of compacted fibrils of a mixture of pulp andcotton linter: 2.5 cm×1.5 cm, 0.3 cm of thickness) is uniformlyimpregnated with 0.5 ml of the above solution to obtain a mosquito-matfor electric heating.

FORMULATION EXAMPLE 12

A solution of 3 parts of the present compound (A) in 97 pars ofdeodorized kerosene is filled in a container made of polyvinyl chloride.Into the container is inserted an absorptive wick made of inorganicpowder solidified with a binder and then calcined, whose upper portioncan be heated with a heater, to obtain a part of a absorptive wick typeelectric heating fumigation device.

FORMULATION EXAMPLE 13

A porous ceramic plate (4.0 cm×4.0 cm, 1.2 cm of thickness) isimpregnated with a solution of 100 mg of the present compound (A) in anappropriate amount of acetone to obtain a fumigant for heating.

FORMULATION EXAMPLE 14

A solution of 100 μg of the present compound (A) in an appropriateamount of acetone is uniformly applied on a filter paper strip (2.0cm×2.0 cm, 0.3 mm of thickness). Then, acetone is vaporized to obtain avolatile agent for using at room temperature.

The following Test Examples will show that the present compound isuseful as an active ingredient for pest controlling agents.

TEST EXAMPLE 1

A solution of 0.025 part of the present compound (A) in 10 parts ofdichloromethane was mixed with 89.975 parts of deodorized kerosene toobtain a 0.025% oil solution.

Adult houseflies (5 males and 5 females) were left in a cubic chamber(70 cm at each side). Into the chamber, 0.7 ml of 0.025% oil solution ofthe present compound (A) prepared above was sprayed with a spray gun ata pressure of 8.8×10⁴ Pa from a small window on the side of the chamber.Two minutes after spraying, the number of the knocked-down insects wascounted (repeated twice).

The same test was carried out except that4-propargyl-2,3,5,6-tetrafluorobenzyl(1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropanecarboxylaterepresented by the formula:

(The compound described as compound 2 in TABLE 1 of EP 0196156 A1;hereinafter, referred to as the comparative compound 1) was used insteadof the present compound (A).

Knock-down ratios, i.e., ratios of the number of knocked-down insects 2minutes after the spraying to the number of tested insects, are shown inTable 1.

TABLE 1 Test compound Knock-down ratio (%) Present compound (A) 100Comparative compound 1 0

TEST EXAMPLE 2

A solution of 0.00625 part of the present compound (A) in 10 parts ofdichloromethane was mixed with 89.99375 parts of deodorized kerosene toobtain a 0.00625% oil solution.

Adult houseflies (5 males and 5 females) were left in a cubic chamber(70 cm at each side). Into the chamber, 0.7 ml of 0.00625% oil solutionof the present compound (A) prepared above was sprayed into the chamberwith a spray gun at a pressure of 8.8×10⁴ Pa from a small window on theside of the chamber. Then, up to 10 minutes after spraying, the numberof the knocked-down insects was counted with time (repeated twice). Thetime required for knocking down 90% of the tested insects (KT₉₀) wascalculated from the results.

The same tests were carried out except for using the comparativecompound 1 and 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl(1R)-trans-3-(2-cyano-1-propenyl)-2,2-dimethylcyclopropanecarboxylaterepresented by the formula:

(The compound described in JP 2004-2363 A; hereinafter, referred to asthe comparative compound 2.).

The results are shown in Table 2.

TABLE 2 Test compound KT₉₀ (minutes) Present compound (A) 2.0Comparative compound 1 Not less than 10 Comparative compound 2 4.3

INDUSTRIAL APPLICABILITY

The present compound is useful as an active ingredient for a pestcontrolling agent.

1. An ester compound represented by the formula (1):


2. A pest controlling agent comprising the ester compound of the formula(1) according to claim 1 as an active ingredient.
 3. A method forcontrolling pests which comprises applying an effective amount of theester compound of the formula (1) according to claim 1 to pests or aplace where pests inhabit.
 4. Use of the ester compound of the formula(1) according to claim 1 as an active ingredient of a pest controllingagent.